Production of color photographic images



United States Patent 3,245,787 PRODUCTION OF COLOR PHOTOGRAPHIC IMAGES Jozef Frans Willems, Wilrijk-Antwerp, and Jan Jaeken,

Hove-Antwerp, Belgium, assignors to Gevaert Photo- Producten N.V., Mortsel, Belgium, a Belgian company No Drawing. Filed Nov. 14, 1960, Ser. No. 71,117

Claims priority, application Great Britain, Nov. 13, 1959,

38,551/ 59 12 Claims. (Cl. 96-9) The present invention relates to the production of colored photographic images, more particularly to a process of color correction utilizing an integral masking procedure.

It is known that dyes formed by color development in substractive multicolor photographic pictures do not transmit all of the light which theoretical considerations demand. The cyan dye which should absorb red light and transmit green and blue light usually absorbs a small amount of green and blue light, as well as a major proportion of red light. The magenta dye which should absorb green light and transmit blue and red light usually absorbs a considerable amount of blue light and a small amount of red light, as well as a major proportion of green light. The yellow dye which should absorb blue light and transmit green and red light is usually satisfactory. I

Due to the above mentioned unwanted side-absorptions of the dyes formed by color development, it is practically impossible to obtain a true reproduction of the original colors on printing multicolor photographic transparencies containing such dyes.

Correction of the colors on printing is therefor desirable, and this is usually done by masking. Since separate masks are difiicult to register with the color trans parency, it is desirable that the mask be integral with the colored images.

A process for the production of a color photographic image wherein the mask is integral with the colored image is described in US. patent applications Ser. No. 705,508, filed December 27, 1957, by Maurice Antoine de Ramaix and Jan Jaeken, now U.S.P. 3,012,884, and Ser. No. 66,944, now US. Patent 3,079,256 filed November 3, 1960, by Raphael Karel Van Poucke, Arthur Henri De Cat and Marcel Hendrik Verbrugghe for process for the manufacture of photographic color images and color correction, and Ger-man patent application G 30,580, filed September 27, 1960, now German Patent 1,119,666.

According to said pending applications a color corrected image is formed in a photographic element comprising a silver halide emulsion layer and a color coupler (more particularly a color coupler of the naphthol type) which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a primary dye image which absorbs a major proportion of light in one region of the visible spectrum (more particularly the red light) and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum (more particularly the green light), by treating the exposed and color-developed photographic element with an oxidizing solution, more particularly a photographic bleaching bath, in the presence of a compound more particularly a 4-amino-pyrazolone-3-compound, which after oxidation couples with the residual color coupler, whereby a secondary dye image having a gradation opposite to that of said primary dye image, and absorbing light in at least one of said unwanted minor absorption regions (more particularly the green light) but transmitting substantially all 3,245,787 Patented Apr. 12, 1966 the light in said major absorption region (more particularly the red light) is formed.

It is an object :of the present invention to provide a new method for correcting the colors of a photographic image used for printing. A further object is to provide a new method for the preparation of an integral mask in color film, more particularly to provide a yellow colored mask image compensating the unwanted absorption of blue light by the magenta image dye. Other objects will appear from the following description and examples.

These objects are accomplished by treating an imagewise exposed photographic element comprising a silver halide emulsion layer and a color coupler which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a primary dye image, after the color forming development, with an oxidizing solution, such as a photographic bleaching bath, in the presence of a compound (called herein.- after mask forming compound) containing a grouping of the following "structure:

R represents a hydrogen atom or an acetyl group,

R represents a hydrogen atom or a functional substituent which is sufliciently unstable for splitting off during the oxidative coupling, such as e.g. a radical of the formula SOg-X or -COX wherein X represents an hydroxyl radical, an amino radical, a substituted amino radical such as a dialkylamino radical, and an N-morpholinyl radical, a hydrocarbon radical or a substituted hydrocarbon radical, such as an alkyl radical e.g. a methyl radical or a cetyl radical, a substituted alkyl radical such as an aralkyl radical and a chloromethyl radical and a carbocyclic radical, e.g. an aryl radical such as e.-g. a phenyl radical, and a substituted aryl radical such as eg a 'p-tolyl radical, a 2,5-dichlorophenyl radical and a 2-decanoylaminophenyl radical, and a heterocyclic radical,

R represents an alkyl radical such as a methyl radical and an ethyl radical, a substituted alkyl radical such as an aralkyl radical and an alkylene radical forming part of a carbocyclic or heterocyclic ring, an aryl radical, a substituted aryl radical, and a radical of the formula SO X or COX wherein X, represents a hydrocarbon radical such as an alkyl radical, a substituted alkyl radical, and a carbocyclic radical such as an aryl radical, and a heterocyclic radical,

L and L each represents a methine group or a nitrogen atom, at least one of L and L being a methine group, and

n is a positive integer from 1 to 2.

According to a preferred embodiment of our present invention, as mask form-ing compounds are used: heterocyclic sulphonyl-, respectively acyl-hydrazones of the wherein Z represents the non-metallic atoms necessary to complete a heterocyclic nitrogen nucleus such as e.g. a benzothiazole nucleus, a benzoxazole nucleus, a benzimidazole nucleus, a thiazoline nucleus, and a 2- quinoline nucleus, and

R and R have the value as set further hereinbefore.

Heterocyclic sulphonyl and acylhydrazones which can be used as mask forming compounds in the process of (13) V the present invention are for instance the compounds the formulae of which are represented as follows:

( JHI 75 wherein n=4, 5,6

H2O N-CH:

I CH3 I CH;

I C H:

The heterocyclic alkylsulfonylhydrazone mask comspounds according to this invention can be prepared ezg. thy usirg one of the following methods.

(1 By condensing a sulfonylchloride compound with an unsubstituted hydrazone.

(2) By reaction df-asulfonylhydrazide'w-ithamethyl- "mercaptocyclammoniumsalt.

PREPARATION .1 N-ethy'Fbenzthiwzvlonc-cetylszilfonylhyiirazone 38.6 g. (0.2 mol) of N-ethylbenzthiozolone hydrazone 'prepared according to K. Fuchs, Ber. -.6-1"p. 59 (1928), and 32.4 g. (0.1 mol) of 'cetylsulfonvlchloride are re- '-fiuxed I together for 2"hours with "600 cm? of 'acetonitrile. The formed precipitate of hydrazone hydrochloride is sucked off when still warm, 'vvhereafter the filtrate is cooled. After recrystallization of the resulted crystals 6 from methanol, 39 g. of N-ethyl-benzthiazolone cetyl sulfonylhydrazone are obtained. Melting point: C.

PREPARATION 2 *N-methyl-quinolone-(Z)-'celylsulf0nylhydraz0ne 2.33 :g. (0.0075 mol) of 1-methy1-2-methylthio-quinovliniurniodide prepared according to O. Fischer, Ber. 35 p. .3677 (1902)., and 2.4 g. (0.0075 mol) of cetylsulfonyl hydrazide are heated for 48 hours at 50 C. with 30 cm. pyridine until the evolution of methylmercaptane has ceased. After pouring out the reaction mixture into wa- :-ter, the obtained solid product is Washed with water and dried and 2 g. of N-methyl-quinolone-(Z)-cetyl sulfonylhydrazone are obtained. Melting point: 101 C. A recrystallization from acetonitrile increases the melting point up to 110 C.

PREPARATION 3 N,N'-dimethyl-benzimidazolone-celylsulfonylhydrazone 9 g. (0.03 mol) of 1-3-dimethyl-2-methylthiobenzimidazoliniummethylsulfate prepared by S. H'tinig. Ann, 609 p. 107 (1957), and 9.6 g. (0.03 mol) of cetylsul fonylhydrazide are mixed at room temperature With 75 cm. of pyridine. After 48 hours the evolution of methylmercaptane has ceased. The reaction mixture is poured into water, the resulting precipitate is Washed With water, sucked-01f and dried. After recrystallization from methanol 5.3 g. of 'N,N'-dimethyl-benzimidazolone-cetylsulfonyl hydrazone are obtained. Melting point: 113 .C.

PREPARATION 4 .N-methy l-benzoxazo lone-cety lsulfonylhydrazone 8.3 g. (0.05 mol) of 2-methylthio-benzoxazole preparedaccordingto S. Hiinig Ann., 609, p. 169 (1957), and 9.3 g. (0.05 mol) of p-tolusulfonic acid methylester are heated for 30 min. at 1500 C. After cooling, the reaction product is Washed with ether. 4.2 g. (0.012 mol) of the obtained tolusulfonate are mixed with 3.9 g. (0.012 mol) cetylsulfonylhydrazide dissolved in 50 cm. pyridine. T he reaction proceeds at room temperature for 24 hours. After pouring out the reaction mixture into .water and Washingwith Water, the obtained product is dried. After recrystallization from methanol the obtained N-methyl-benzoxazolone cetylsulfonylhydrazone melts at9'8 C.

PREPARATION 5 N-methyl-thiozolinone-cetylsulf0nylhydraz0ne 1.38 g. (0.005 mol) of 2-methy1thio-3-methyl-thiazoliniuniiodide and 1.6 g. (0.005 mol) of cetylsulfonylhydraz'ide are mixed and heated for 24 .hours at 50 C. with .15 cm. of pyridine and 1.5 cm. of piperidine. After pouring out into Water, the reaction product is washed withwater and dried. The'hydrazone thus obtained .is recrystallized from methanol. 1.7 g. of N-methyl-thiazolinone-cetylsulfonylhydrazone are obtained. Melting point: 98 C.

PREPARATION :6

.N-ethyl-b enzthiozdlone-(m-decanoylamino phenyl)r sulfonylhydrwzone 3816: g. (0.2 mol) of N-ethyl-benzthiozolonehydrazone :preparedaocording to K. Fuchs, Ber. 61, ,p. 59 (1928),

.443 1g. (0.2 mol) of .rn-nitrobenzene sulfochloride and 34.5. (0.4 mol) -.of;anh ydrous sodiumacetate are mixed with 600cm. of acetonitrile and refluxed for 2 hours. 1" he reactionrnixture is poured out-into water. Thesolid product obtained is Washed With water, separated and dried. 62 g. of.N-ethylbenzthiozolone-(m-nitrophenyl) sulfonylhydrazone areobtained. Melting point: 222 C. 'A recrystallization of vacetonitrile does not increase the melting point. 18.9.g. (0.05 mol) of the obtained hydrazone are dissolved in cm. of dioxane, 150 cm. of

acetic acid and 30 cm. of water. The reduction is carried out at boiling temperature by portion-wise adding 17 g. of iron-filing. After adding, the reaction mixture is further heated for 30 min. Then the reaction mixture is poured out into water, the solid product is washed with water and dried. 16 g. of N-ethyl-benzthiazolone-(maminophenyl)-sulfonylhydrazone are obtained. Melting The process of color correction of the present invention may be practiced, i.e., by using a color photographic material containing a coupler for magenta belonging to the class of the pyrazolone or indazolone color couplers and/ or a coupler for cyan belonging to the class of the phenol or naphthol color couplers. Depending upon the structure of the color coupler used in combination with the hydrazone mask-forming compound according to the present invention, yellow to magenta colored mask images are obtained on treating the photographic material with an oxidizing substance such as. present in a ferricyanide bleaching bath.

According to a preferred embodiment of the present invention, the hydrazone mask forming compound is incorporated in one of the layers present in the light-sensitive photographic material, preferably in the silver halide emulsion layer wherein the mask image is to be formed by oxidative coupling of the residual color coupler present in that layer with the mask forming substance; in order to prevent the diffusion of the mask forming compound out of the silver halide emulsion layer wherein this compound originally was incorporated, preferably. hetero cyclic sulfonyl or acyl hydrazone mask formingcompounds are used containing a radical (e.g. the radical X and/or X in the above formula) comprising a linear chain of 5 to 20 carbon atoms.

For carrying out the process according to the present invention, the color couplers and mask compounds can be incorporated into a photographic silver halide emulsion prepared by means of the colloids usually employed therefor such as for instance gelatin, polyvinyl alcohol, collodion or other natural or synthetic colloids. The silver halide emulsion can be cast to a support consisting of paper, glass, nitrocellulose, cellulose esters such as cellulose t-riacetate, polyester, polystyrene or another natural or synthetic resin, and form part of a photographic material 'with one or more emulsion layers. The multilayer material usually comprises the following elements: a sup the light-sensitive emulsion layer by a water-permeab1e colloid layer.

The following aromatic amino-compounds can 'be used as developers for such material: mono-, diand tria'minoaryl compounds, more especially N,N-dialkyl-p-phenylene- .diamines, such as N,N-diethy1-p-phenylenediamine and N,N-diethyl-2-methyl-p-phenylenediamine, and derivatives into a non-light-sensitive layer which is separated from thereof such .as N,N-dialkyl-N-sulphomethylor carboxymethyl-paphenylenediamine. As useful monoaminodevelopers should be citedz: aminophenols and aminocresols or their halogen derivatives and also the aminonaphthols.

The following examples illustrate the invention without limiting, however, the vscopethereof.

EXAMPLE 1 To /z kg.;of a greensensitized silver bromo-iodide emulsion containing /6 mol of silver halide is added a slightly alkaline alcoholic solution containing 9 g. of 1-p-sulfo phenyl-3-heptadecyl-5-pyrazolone and 6 g. of 3-ethyl-Z-benzthiazolone-[i-cetylsulphonyl hydrazone of the following formula:

dissolved by heating in alcohol/water (1:3) with a little sodium hydroxide; After acidification with acetic acid to pH 6 and after addition of the usual additives such as hardeners, Wetting agents and stabilizers, the emulsion obtained is coated on a suitable support and dried. After exposure through a grey wedge witha constant 0.15, the photographic material is developed for 9 minutes at 20 C. in a color developing bath with the following composition:

G. Sodium. hexametaphosphate 2 N,N-diethyl-p-phenylenedia.mine hydrochloride 3 Sodium sulphite 4 Sodium canbonate 57 Hydroxylamine hydrochloride 1.5 Potassium bromide 1 Water to 1000 cm (pH=10.6).

This material is rinsed for 30 minutes at 18 to 20 C. and fixed for 5 minutes at-20 C. in a fixing bath of the following composition:

Sodium thiosulphate 200 Sodium bisulphite 25 Potassium alum 20 Sodium biacetate 20 Boric acid 7.5 Water to 1000 cm. (pH=4)..

Next, the material is rinsed again for 10 minutes at 18 to 210 C. and treated for 5 minutes in a bleaching bath of the following composition:

G. Potassium ferricyanide Potassium bromide 15 Borax 20 Magnesium sulphate 50 Water to 1000 cm. (pH=8.6).

Rinsing is continued for another 10 minutes at 18 to 20 C. and then the material is fixed again for 5 minutes at 20 C. 1n a bath of the following composition:

18 to 20 C. and the material is dried.

A mainly magenta colored-image is; obtained together with a yellow dye image, said yellow image being of opposite gradation in respectof theamagenta dye image and reducing the disturbing. influence of the side absorptions' in the formed magenta image.

9: EXAMPLE 2- 'To /2 kg, of a green-sensitized silver bromo-iodide emulsion containing: mol of. silver halide. is added a slightly alkaline. alcoholic: solution containing 9 g; of 2;- (1 -v phenyl: 5 L oxo-3rpyrazolinylimino') -3l-carbethoxy- 111p( 1-cetyloxy).-phenyl],-thiazoline, and 6. g., of 3-ethyl- 2-benzthiazolone-dcetylsulphonyl hydrazone of the tollowingformula; 3

dissolved by heating. in alcohol/water (1:3) with a: little sodium hydroxide. After acidification with acetic acid to pH 6 and after addition of the usual additives; such as hardeners, wetting agents and stabilizers, the emulsion obtained is ready to be coated. After coating this emulsion. forms part of a. multilayer photographic material consisting of the following superposed layers in the indicated sequence: a support, an antihalati'on layer, a gelatin insulating layer, a red-sensitized emulsion layer with color coupler for cyan, a gelatin interlayer, the above-mentioned green-sensitized emulsion layer, a yellow filter layer, a

blue-sensitive emulsion layer with color coupler for-yellow and at least a gelatin overcoat as antistress layer.

After exposure through a grey wedge with a constant 0.15 the photographic material is developed and further treated'as in Example 1.

A mainly magenta colored image is obtained together with a yellow dye image in the green-sensitized layer, said yellow image being of opposite gradation in respect of the magneta dye image and reducing the distributing influence of the side-absorptions in the formed magenta image.

We claim:

1. In a method of forming a color corrected image in a photographic element having at least one silver halide emulsion layer containing a color coupler for magenta which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a magenta primary dye image which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, in which method said element is exposed to said image to be photographed, developed with said developing agent and thereafter treated with an oxidizing solution, the improvement which comprises carrying out said development and said treatment in the piesence of a mask forming compound having the formula:

wherein:

R is a member of the group consisting of a hydrogen atom and an acetyl group,

R is a member of the group consisting of an alkyl radical and an aryl radical,

Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing 56 members, at least one of which is a nitrogen atom, and

X is a member of the group consisting of an hydroxyl radical, an amino radical, an alkyl radical, an aryl radical, and a heterocyclic radical;

whereby the residual color coupler oxidatively couples with said mask-forming compound to form a secondary dye image having a gradation opposite to that of said magenta primary dye image, said secondary image absorbing light in at least one of said undesirable minor ab- 10' sorption regions but transmitting substantiallyall the. light in said major absorption region.

2. The method of claim 1 wherein said color coupler for magenta is a member of the group consisting oi the pyrazol'one and indazolone' color couplers.

3.. The method of claim 1 wherein, said; masl'r forming compound is incorporated in the photographic element and the oxidizing solution is a photographic bleaching bath.

4. The method of claim 1 wherein said? mask-forming compound", is present in at least said one layer containing said color coupler; I

5. The method of claim 1 wherein: said] mask-forming compound forms a. yellow secondary dye image.

A color photographic-element useful in the method of claim 1; said element having superposed silver halide emulsionlayers, sensitive, to dilferent regions of the visible spectrum, at least one ofsaid layers containing a-color coupler for magenta which is reactive with the oxidation product of an aromatic amino developing agent; to form by color development a magenta primary d'ye image which absorbs a major proportion of light in one region of the spectrum, and undesirably absorbs a minor proportion'of light in at least one other region of the visible spectrum, such layer also containing a mask'forming compound of the formula:

wherein:

R is a lower alkyl radical,

Z represents the non-metallic atoms necessary to complete a heterocyclic nitrogen nucleus, and

X is an organic radical comprising a linear chain of 5 to 20 carbon atoms free of ethylenic unsaturation,

said color coupler for magenta also being reactive with the oxidation product of said mask-forming compound to form a secondary dye image having a gradation opposite to that of said magenta primary dye image, and absorbing light in at least one of said unwanted minor absorption regions but transmitting substantially all the light in said major absorption region.

7. In a method of forming a color corrected image in a photographic element having at least one silver halide emulsion layer containing a color coupler for cyan which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a cyanprirnary dye image which absorb-s a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, in which method said element is exposed to said image to be photographed, developed with said developing agent and thereafter treated with an oxidizing solution, the improvement which comprises carrying out said development and said treatment in the pressure of a mask-forming compound having the formula:

wherein:

R is a member of the group consisting of a hydrogen atom and an acetyl group,

R is a member of the group consisting of an alkyl radical and an aryl radical,

Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing 56 members, at least one of which is a nitrogen atom, and X is a memebr of the group consisting of a hydroxyl bath.

wherein:

,ical, and a heterocyclic radical;

whereby the residual color coupler oxidatively .couples with said masloforming, compound to form a secondary dye imagehaving a gradation opposite to that of said cyan primary dye image, said secondary image absorbing light in at least one of said undesirable minor absorption regions but transmitting substantially all the light in said major absorption region.

8. The method of'claim 7 wherein said color coupler for cyan is a member of the group consisting of the phenol and napt hol color couplers.

9. The method of claim 7 wherein said mask-forming compound is incorporated in the photographic element and the oxidizing solution is a photographic bleaching 10. The method of claim 7 wherein said mask-forming compound is present in at least said one layercontaining said color coupler.

11. The method of claim 8 wherein said'mask-forming compound forms a magenta secondary dye image.

12. A color photographic element useful in themethod of claim 7, said element having superposed silver halide emulsion layers sensitive to different regions of the visible said layers containing a color 12 R is a lower alkyl radical, Z represents the non-metallic atoms necessary to complete a heterocyclic nitrog'enLnucleus, and X is an organic radical comprising a linear chainof 5 to 20 carbonatoms free of ethylenic unsaturation,

said color coupler for cyan also being reactive with the oxidation product of said mask-forming compound to form a'secondary dye image having a gradation opposite to that of said cyan primary dye image, and absorbing light in at least one of said unwanted minor absorption regions but transmitting substantially all the light in said major absorption region.

References Cited by the Examiner UNITED STATES PATENTS 2,396,396 3/1946 Stamrners 9655 2,527,476 10/1950 Bruylants et a1 9655 2,895,825 7/1959 Pelz et a1. 96-55 3,012,884 12/1961 'De Ramaix et al. 9655 X 3,028,237 4/1962 Lofiier 969 3,047,385 7/ 1962 De Ramaix et al 969 FOREIGN PATENTS 685,061 12/1952 Great Britain. 790,327 2/ 1958' Great Britain.

uct of an aromatic amino developing agent to form by color development a cyan primary dye image which absorbs a major proportion of light in one region of the spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, such layer also containing a mask-forming compound of the formula:

N ORMAN G. TORCHIN, Primary Examiner. HAROLD NJBURSTEIN, Examiner.

R. A. BURROUGHS, 1.1T. BROWN,

" Primary Examiners. I 

1. IN A METHOD OF FORMING A COLOR CORRECTED IMAGE IN A PHOTOGRAPHIC ELEMENT HAVING AT LEAST ONE SILVER HALIDE EMULSION LAYER CONTAINING A COLOR COUPLER FOR MAGENTA WHICH IS REACTIVE WITH THE OXIDATION PRODUCT OF AN AROMATIC AMINO DEVELOPING AGENT TO FORM BY COLOR DEVELOPMENT A MAGENTA PRIMARY DYE IMAGE WHICH ABSORBS A MAJOR PROPORTION OF LIGHT IN ONE REGION OF THE VISIBLE SPECTRUM, AND UNDESIRABLY ABSORBS A MINOR PROPORTION OF LIGHT IN AT LEAST ONE OTHER REGION OF THE VISIBLE SPECTRUM, IN WHICH METHOD SAID ELEMENT IS EXPOSED TO SAID IMAGE TO BE PHOTOGRAPHED, DEVELOPED WITH SAID DEVELOPING AGENT AND THEREAFTER TREATED WITH AN OXIDIZING SOLUTION, THE IMPROVEMENT WHICH COMPRISES CARRYING OUT SAID DEVELOPMENT AND SAID TREATMENT IN THE PRESENCE OF A MASK FORMING COMPOUND HAVING THE FORMULA: 